CH656136A5 - COMPOSITION BASED ON POLYOLEFINS. - Google Patents

Description

The present invention relates to novel compositions based on polyolefins and also relates to particular applications of these compositions.

Polyolefins (polyethylene, polypropylene, etc.) are used with advantage in a large number of applications. However, it is known that they are not completely satisfactory for certain applications requiring impact resistance, dye affinity, ability to be painted or anti-static properties for example.

It has therefore been sought for a long time to improve the impact resistance properties of the products obtained by molding, extrusion or injection of polyolefins, such tubes, or materials intended for automobile, electric, etc. We also try to improve their dye affinity and their ability to be painted, if only to give them certain colors allowing the use of these materials for construction and decoration. Similarly, it has long been sought to dye certain polyolefins, such as polypropylene, which so far cannot be dyed satisfactorily.

The present invention overcomes the aforementioned drawbacks. Indeed, it makes it possible to confer on new products based on polyolefins impact resistance properties, and therefore to widen the spectrum of use of polyolefins. In addition, it makes it possible to obtain products based on polyolefins having various colorings and improved antistatic properties.

The present invention is based on the surprising and unexpected observation that polyolefins are completely miscible with certain defined compounds and that the compositions formed from a mixture of polyolefins and of said compounds have improved properties of impact resistance at low temperature, of antistatism. and dye affinity.

The subject of the present invention is a composition formed by an intimate mixture of one or more polyolefins and one or more polyetheresteramides, and optionally containing organic or inorganic fillers, said mixture being formed from 1 to 99% by weight of polyolefin and of 99 to 1% by weight of polyetheresteramide.

The term “polyetheresteramides” is intended to mean both statistical polyetheresteramides (that is to say formed by the random sequence of the various monomer components) as well as sequenced polyetheresteramides, that is to say formed from blocks having a certain length chain of their various constituents. Polyetheresteramides are, as is known, copolycondensates of polyamide sequences at the end of the dicarboxylic chain with either polyetherdiol sequences, or polyetherdiamine sequences or copolycondensates of polyamide sequences at the end of the diamino chain with polyether sequences at the end of the carboxylic chain.

Such products have been described in French patents Nos 7418913 and 77 26678, the content of which must be added to the present description.

According to one embodiment of the invention, the polyamide sequences of the polyetheresteramides are preferably formed of polyamide 6, 6.6, 6.12, 11 or 12 (PA-6, PA-11, PA-6.6, PA-6.12, PA -12) or copolyamides resulting from the polycondensation of their monomers.

Preferably, the molecular weight of these polyamide sequences is between 500 and 10,000 and, more particularly, between 600 and 5000.

According to another embodiment of the invention, the polyether blocks consist of polytetramethylene glycol (PTMG), polypropylene glycol (PPG), or polyethylene glycol (PEG). Preferably, the molecular weight of the polyethers is between 150 and 6000 and, more particularly, between 400 and 3000.

According to yet another embodiment of the invention, the aforementioned polyetheresteramide is formed from 5 to 85% and, more particularly, from 30 to 80% of polyether and from 95 to 15% and, preferably, 70 to 20% of polyamide.

According to one embodiment of the invention, the polyolefin consists of polypropylene (PP), polyethylene (PE), their mixtures or copolymers or the ionomer resins sold under the name Surlyn "from the company DuPont de Nemours. Preferably , said mixture is formed from 70 to 97% of polyolefin and from 30 to 3% of polyetheresteramide.

The organic or mineral fillers that said composition may contain consist of the usual fillers such as silica, titanium oxide, talc, mica, kaolin, magnesia, glass fibers, carbon black, vermiculite, glass beads, calcium carbonate, fibers carbon, used in combination with polymer compositions.

Of course, said compositions may contain the usual additives such as anti UV, heat or light stabilizers, release agents, etc.

The process for obtaining these compositions consists in mixing the two raw materials in powder or granular dry form and in treating the mixture obtained in an extruder, single screw or twin screw or in kneading machines such as Ban-

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656,136

burry ", Buss mixer" or in calendering devices such as calendering screws, etc. It is also possible to operate, by mechanical mixing, in the hopper of the extruders or injection presses prior to extrusion or injection.

The present invention also relates to the applications of said compositions, in particular for the production of objects by molding, extrusion, injection, impact resistant and antistatic. It also relates to the shaped objects and in particular to the tubes, films, seeds, etc., obtained from these compositions and, in the alternative, to the colored or painted shaped products obtained from these compositions.

Other objects and advantages of the present invention will appear on reading the following description and examples given without limitation.

Examples 1 to 4:

The operation is carried out in a Werner Pfleiderer twin screw extruder, the screw rotation speed of which is 50 rpm.

The extruder output is 20 kg / h. The temperature profile in the extruder is 225-230-240-230 ° C from the inlet to the outlet.

As polyolefin used in these examples, polypropylene homopolymer of grade 3020 SN-3 manufactured and sold by the company Ato Chimie whose melt index (MI) = 8 (determined at a temperature of 230 ° C. under a load 5 kg).

The polyetheresteramide used is formed from 30% of PA-12 of molecular weight 850 approximately and of 70% of PTMG whose molecular weight is approximately 2000.

The polyolefin / polyetheresteramide weight ratios in the compositions prepared according to these examples 1 to 4 are respectively 95/5, 90/10, 85/15 and 80/20.

The physical properties of the compositions obtained are determined on test pieces obtained from these compositions and the results are reported in Table I.

Example 5:

s With the same polyolefin as that used in Examples 1 to 4, and operating under the same conditions, a polyetheresteramide formed from 50% of PA-12 of molecular weight 2000 and 50% of PTMG of molecular weight is combined 2000.

The polypropylene / polyetheresteramide weight ratio is 90/10.

The physical properties of the composition obtained, determined on test pieces assembled from these compositions, are recorded in Table I.

, 5 Examples 6 and 7:

With the same polyolefin as that used in Examples 1 to 4 (namely polypropylene of grade 3020 SN-3) and operating under the same conditions, a polyetheresteramide formed of 68% PA-6 of molecular weight is combined equal to approximately 1300 to 32% of PPG with a molecular weight of the order of 600.

The polypropylene / polyetheresteramide weight ratios are 90/10 (example 6) and 85/15 (example 7) respectively.

The physical properties determined on test pieces obtained from these compositions are shown in Table I.

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Example 8:

The operation is carried out under the same conditions as those described in Example 5, except that the polyetheresteramide is formed from 50% of PA-6 of molecular weight of the order of 1500 and from 50% of PEG of molecular weight equal to approximately 1500.

The physical properties determined on test pieces obtained from these compositions are shown in Table I.

Table I

Example

1

2

3

4

5

6

7

8

9

. io

Melt index

5

5.5

6

6.4

5

4

4

5

5

4

Density

0.910

0.915

0.920

0.925

0.915

0.925

0.930

0.925

0.905

0.895

Flexural modulus

13,500

12700

12000

11700

13000

14000

13,500

13000

15000

12,500

Choc Izod 23 e C OC

20 10

60 17

N.C. * 20

N.C. * N.C. *

40 13

15

8

20 10

35 12

4.5 2.5

50 15

Shore D hardness

63

61

60

58

63

65

63

63

70

61

Vicat temperature

147

144

142

140

148

151

150

150

152

143

* N.C. = does not break.

Example 9:

As a control example, the operation is carried out under the same conditions as those described in Examples 1 to 4, without adding the polyetheresteramide to the olefin used, this olefin consisting of propylene homopolymer sold by Ato Chimie under reference 3020 SN-3.

The physical properties determined on a test piece are recorded in Table I.

Example 10:

Also as a control example, the procedure is the same as that described in Examples 1 to 4, without adding polyetheresteramide and using polypropylene of "hyper shock" grade sold by Ato Chimie under the reference 3040 MN6.

Table I contains the results of the determinations carried out on a test piece obtained from this composition.

Table I contains the results of the determinations carried out on test pieces obtained from the compositions according to Examples 1 to 10.

It can be seen from the analysis of these results and from the errors of experience, that:

the Shore hardness of the test pieces obtained from the compositions according to the invention is less than the Shore hardness of the homopolymer polypropylene of Example 9 and equivalent, on average, to that of the "hyper impact" polypropylene copolymer of Example 10; The Vicat temperature of the test pieces obtained from the compositions according to the invention is generally between the Vicat temperature of the "hyper impact" copolymer of Example 10 and the Vicat temperature of the homopolymer of Example 9;

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the elasticity moduli of the test pieces of the compositions according to examples 1 to 8 are between those of the test pieces of the “hyper impact” copolymer of example 10 and of the homopolymer of example 9;

the densities are higher, for the compositions according to the invention of Examples 1 to 8, than those of the densities of controls 9 and 10;

the impact strengths at 23 ° C. and at 0 ° C. of the test pieces of Examples 1 to 8 are very much higher than that of the test pieces of Example 9 and in most cases than that of Example 10.

Furthermore, antistatic measurements were carried out on molded masses obtained from the compositions according to examples 1 to 10. The test for assessing the antistatic power consists in developing by friction electrostatic charges, under conditions always identical and assess the charge thus created by the cigarette ash test.

It is noted, apart from experimental errors, that the products of Examples 1 to 8 have antistatic properties clearly superior to those of the products of Examples 9 and 10.

In addition, radio sets were made by molding from the compositions of Examples 1 to 10. These sets are immersed in a hydroacetic solution at 80 ° C contained in a dye tank. This hydroacetic solution has the following composition:

AJL dimacid blue 3%

Sunaptol 0.1%

80% acetic acid up to pH 5

After 1 hour of immersion, the boxes are removed from said tank and rinsed.

It is found that the boxes obtained from the compositions according to Examples 9 and 10 are not dyed, the dye not having "hung" on the material from which they are formed. On the other hand, in the cases of boxes obtained from compositions 1 to 8, a dark blue coloring is obtained.

Examples 11 to 15:

The operation is carried out according to the same method as that described in Examples 1 to 4, the polyolefin consisting of Lacqtene1 1055 MN-20 (low density high pressure polyethylene manufactured by the company Ato Chimie) and the polyetheresteramides being as indicated in the Table II in which is also indicated the Lacqtèneïï7polyêtherestêramide weight ratio employed.

Table II

Example

11

12

13

14

15

Polyetheresteramide - polyamide molecular weight

PA-12,800

PA-12 2850

PA-6 4200

PA 7900

-

- polyether molecular weight

PTMG 1800

PTMG 2000

PPG 4200

PPG 1600

-

- polyamide / Lacqtene polyether /

polyetheresteramide

30/70 95/5

40/60 90/10

68/32 90/10

50/50 85/15

100/0

The physical properties of the products obtained from these compositions are determined and it can be seen that the impact resistance, the antistatism and the dye affinity are markedly improved for the products obtained from the compositions according to Examples 11 to 14 by comparison with the Lacqtène * of Example 15.

Examples 16 to 19:

Mixtures identical to those of Examples 2, 9, 11 and 15 are respectively prepared, to which a charge consisting (expressed in weight proportions) of 30% glass fibers, having a length of the order of 1 mm, is added.

Radio covers are made from these mixtures by molding. On these covers, a layer of commercially available gray glycerophthalic lacquer is applied by spraying. After drying, it is found, using the tape test, that the paint layer adheres to the covers obtained from the compositions of Examples 17 and 19 [formed respectively from pure polypropylene (from Example 9) and pure polyethylene (from Example 15) loaded with glass fibers] do not give rise to a “catching” of the paint layer.

In the foregoing, convenience has been denoted by their current commercial name polytetramethylene glycol, polyethylene glycol and polypropylene glycol, which corresponds according to the official nomenclature to polyoxytetramethylene glycol, polyoxyethylene glycol and polyoxypropylene glycol.

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Claims (12)

656136 1% by weight of polyetheresteramide. 1. Composition formed by an intimate mixture of one or more polyolefins and one or more polyetheresteramides, said mixture being formed from 1 to 99% by weight of polyolefin and from 99 to 2. Composition according to claim 1, characterized in that the polyetheresteramides are random polyetheresteramides. 2 3. Composition according to claim 1, characterized in that the polyetheresteramides are copolycondensates of polyamide sequences at the end of the dicarboxylic chain with either polyetherdiol sequences or polyetherdiamine sequences, or copolycondensates of polyamide sequences at the end of the diamino chain with polyether blocks for carboxylic chain ends. 4. Composition according to one of claims 1 to 3, characterized in that the polyamide blocks of the polyetheresteramides are formed of polyamide 6, 11, 6.6, 6.12 or 12 respectively designated by PA-6, PA-11, PA-6.6, PA- 6.12, PA-12 or copolyamide resulting from the copolycondensation of their monomers. 5. Composition according to claim 4, characterized in that the molecular weight of the polyamide blocks is between 500 and 10,000 and, more particularly, between 1000 and 5000. 6. Composition according to one of claims 1 to 3, characterized in that the polyether blocks consist of polyoxytetamethy-lene glycol PTMG, polyoxypropylene glycol PPG or polyoxyethy-lene glycol PEG. 7. Composition according to claim 6, characterized in that the molecular weight of the polyether blocks is between 150 and 6000 and more particularly between 400 and 3000. 8. Composition according to one of claims 1 to 7, characterized in that the aforementioned polyetheresteramide is formed from 5 to 85%, and more particularly from 30 to 80%, of polyether and from 95 to 15%, and preferably 70 to 20 %, of polyamide. 9. Composition according to one of claims 1 to 8, characterized in that the polyolefin consists of polypropylene PP, polyethylene PE, their mixtures or copolymers or in ionomer resins. 10. Composition according to one of claims 1 to 9, characterized in that said mixture is formed from 70 to 97% of polyolefin and from 30 to 3% of polyetheresteramide. 11. Composition according to one of claims 1 to 9, characterized in that it contains an organic or inorganic filler consisting of fillers such as silica, titanium oxide, talc, mica, kaolin, magnesia, glass fibers, carbon black , vermiculite, glass beads, calcium carbonate, carbon fiber and, optionally, additives such as anti UV, heat or light stabilizers, release agents. 12. Shaped objects obtained from the composition according to one of claims 1 to 10.